KR19990008457A - Manufacturing method of high viscosity resin - Google Patents

Abstract

The present invention discloses a process for producing a high viscosity gelling ink resin exhibiting improved properties. In a preferred embodiment, the precursor resin is reacted with a crosslinking agent, preferably a thermally reactive phenolic resin, via an extruder to induce covalent crosslink formation in the resin, producing a high viscosity resin that withstands viscous breakage under high shear conditions. The resulting gelled ink resin can be used to prepare the ink directly, and the need for further gelation is avoided in advance, and there is no need to use conventional organometallic crosslinkers.

Description

Manufacturing method of high viscosity resin

The present invention generally relates to an ink resin and a method for producing the ink resin. In particular, the present invention relates to a process for the preparation of very high molecular weight, highly crosslinked ink resins and to improved resins produced by the process.

Conventional rosin and hydrocarbon based resins used in the lithographic ink sector are produced in stirred tank reactors. Relatively low melt viscosities and slow reaction rates are ideally suited for this type of device. Often, a reaction time of about 24 hours is required to obtain a product of the desired properties. Such resins are generally highly branched and have a very wide molecular weight distribution. The product may contain some crosslinked gel structures, but when using a stirred tank reactor the amount of the gel structures may not be able to handle the non-Newtonian behavior and very large melt viscosity that accompanies the presence of the gel resin structure. The amount is typically limited. Thus, if a very highly structured material is desired, such resins are typically gelled in a separate gelling reaction in solution to improve the flowability of such resins.

Conventional lithographic ink vehicles can be prepared by dissolving / dispersing existing resins in a lithographic ink solvent and so-called gelling reaction of the mixture with a crosslinking agent based on aluminum. Aluminum compounds in the manufacture of lithographic ink vehicles have typically played a role in controlling the ink vehicle fluidity.

Known aluminum gelling compounds used to prepare ink vehicles can be classified as follows: 1) aluminum salts, 2) aluminum alkoxides, 3) chelated alkoxides and 4) oxyaluminum acylates. However, aluminum hydroxyl functionality needs to be created or present for the aluminum compound to form the ultimate fluidity or gel structure. Thus, the resulting gel structure is the result of coordination covalent or hydrogen bonding of aluminum hydroxyl groups.

Coordination covalent bonds and hydrogen bonds are relatively weak bonds, typically about 5 to 10% of the bond of the covalent bond. Under the high shear conditions associated with lithography, the gel structure due to this bonding actually degrades. Some degree of thixotropic behavior is important for successful printing. However, there is a limit to the degree of flow development that can be tolerated before unwanted side effects occur. As the printing speed increases, the loss of gel structure becomes even more important.

One of the consequences of loss of gel structure in ink vehicles is the tendency for excessive mist to develop. The tendency for mist to occur is increased as the roller device speed of the printing press increases and more and more shear force is applied. This tendency of misting is compounded by the loss of viscosity due to the destruction of the gel structure that occurs when the printing speed is high.

Another deterioration of the ink structure and viscosity due to excessive shear forces is a loss of print clarity. If the ink is sheared to such an extent that the flow of the ink is severe, the printed dots spread, resulting in excessive dot increase or inferior print quality.

Another problem associated with the use of gelling agents is that manufacturers of ink vehicles shift to using solvents from renewable raw materials and solvents that significantly lower the levels of volatile organic compounds (VOCs) in the ink. Examples of such solvents are various fatty acid esters. Fatty acid ester solvents generally have a greater solvation power than the resins used to prepare the gelled ink vehicles, but typically do not provide the same level of resin loading as compared to solvents of the hydrotreated petroleum distillate type. It is more difficult to obtain a strong gel structure with existing resins. Increased solvation forces make it more difficult to obtain the desired strong gel structure that requires the use of more crosslinking agents in the production of products with less resistance than optimum resistance to shear induced breakdown.

Another undesirable aspect of using gelling agents is that these gelling agents are typically the most expensive components in varnish formulations, based on weight percent. Gel reactions also require a separate reaction step to prepare the gelling ink vehicle, thus consuming time, energy and attraction. Thus, the use of organo-aluminum gelling agents is clearly economically disadvantageous.

Moreover, the lithography industry is turning to using higher molecular weight / high solution viscosity self-structuring ink resins to improve the printing performance of the ink during high speed printing operations. The new generation of web-offset lithography machines can achieve print speeds of less than about 914.4 meters / minute (3,000 feet / minute). However, the range of crosslinkable resins achievable in stirred tank reactors as described above is limited by the ability to stir, adjust or otherwise process the final product having a very high melt viscosity. Reducing the level of crosslinked resin typically reduces the solution viscosity level and the degree of self-structuring of the resin.

With the tendency to print faster and the continuing desire to improve the ink application process and print quality, there has been a continuing need for improved resins for use as ink vehicles in the printing industry. Under the high shear intense printing conditions of current high speed printing machines, it is one important goal to develop a high viscosity resin that allows the final ink to exhibit good mistability.

It is therefore an object of the present invention to provide a high viscosity ink resin and a process for producing the ink resin which avoids the disadvantages of the conventional process.

It is another object of the present invention to provide a high viscosity ink resin which reduces the misting in a high speed printing press.

Furthermore, it is an object of the present invention to provide high viscosity resins for use in lithographic ink formulations in order to improve the properties of the formulations.

It is a further object of the present invention to provide a process for the preparation of resins characterized by readily available and relatively inexpensive materials.

Another object of the present invention is to provide a method for producing a resin, characterized in that the price is practical and not complicated.

It is a further object of the present invention to provide a process for the preparation of high viscosity resins which enables improved control over the properties of the resin and enables improved uniformity over the properties of large amounts of resin.

It is still another object of the present invention to provide a method for producing a high viscosity resin for high speed printing, which maintains high viscosity even under the intense conditions associated with high speed printing.

In view of the above and other objects, the present invention relates to a method for producing a high viscosity ink resin. In a broad sense, this process reacts rosin or hydrocarbon based resins with certain nonmetallic containing crosslinkers, resulting in crosslinking with substantially increased viscosity, resulting in improved stability against mechanical breakage imparted to the material during printing operations. Forming covalent crosslinks in the ink resin composition. The resulting crosslinked resin has a practical gel content characterized by the preponderance of covalent crosslinking. Rosin or hydrocarbon based resins that are crosslinked are sometimes referred to herein as precursor resins.

In particular, it has been found in the present invention that gelled ink resins prepared by the method of the present invention provide stable high viscosity for varnish inks and formulations containing resins even under high shear conditions. Thus, the resins produced by the process of the present invention have much improved mist properties, because commercially available resins tend to lose viscosity and elasticity when subjected to harsh mechanical and thermal stresses. This is because the resin can maintain higher viscosity and elasticity even under these conditions.

According to another aspect of the present invention, there is provided a method of producing an ink resin comprising introducing a precursor resin selected from the group consisting of rosin and hydrocarbon based resins into the inlet of an extended reaction chamber. The precursor resin continues to mix vigorously with the crosslinking agent as it proceeds continuously from its inlet end toward the outlet through the reaction chamber to form covalent crosslinks in the precursor resin under the application of sufficient thermal energy to the mixture. The amount of crosslinker is typically from 0.5% to 10.0% based on the total amount of reactants of the precursor resin and the crosslinker. Sufficient heat energy is mixed into the mixture when it is mixed and passed through the reaction chamber to form a covalent crosslink in the mixture, and then passes through the outlet from the reaction chamber. By this method, a crosslinked ink resin having a Gardner bubble viscosity of at least about 150 bubble seconds can be produced at 38 ° C.

According to the present invention, the Gardner bubble viscosity of the resulting resin was determined by dissolving the resin in linseed oil or MAGIESOL 47. For the rosin base resin, the Gardner bubble viscosity of the ink resin was measured using a 33.3 wt% resin solution in linseed oil. For hydrocarbon based resins, Gardner bubble viscosity was measured using a 50 wt% resin solution in MAGIESOL 47.

Particularly preferred extended reaction chambers for carrying out the process of the invention are extruders, more preferably twin screw extruders. A reaction time of only about 30 seconds to about 15 minutes is obtained for the viscosity of the resin solution of about 1000% or less. The resulting high viscosity covalent crosslink product from the extruder can be combined with other components to form an ink varnish that can be used as the vehicle in an ink formulation for a high speed printer, preferably a lithographic printer.

As used herein, the term rosin and hydrocarbon based resins refers to functionalized cyclic and dicyclic unsaturated hydrocarbon resin compounds and natural derivatives derived from hydrocarbon raw materials containing from about 5 to about 15 carbon atoms, which are widely utilized in ink preparation. It will be understood to include any one of resins, as well as numerous functionalized rosin based resins used in ink production.

The term rosin as used herein will be understood to include gum rosin, wood rosin and tall oil rosin. Rosin is obtained from pine (mainly pinus palustris and pinus elliottii ). Gum rosin is the residue obtained after distillation of terebin oil from oleoresin, which receives liquid from live pines. Wood rosin is obtained by extracting pine roots using distilled naphtha or other suitable solvent and distilling off the volatilization fraction. Tall oil rosin is a byproduct of the fractionation of tall oil, a by-product of wood pulping. The main components of rosin are rosin acids of Aviet and Pima series. Rosin acid has the formula C ₁₉ H ₂₉ COOH with a phenanthrene nucleus. Preferred rosin used in the present invention is tall oil rosin.

Rosin is used in a limited amount in ink in its natural state. The main use of rosin is to be used as raw material for preparing chemically modified rosin derivatives for various end uses. Important modified rosin and rosin derivatives used in the production of printing inks include polymers or dimer rosins and their esters, metal resinates, phenols and / or maleic / fumaric acid modified resins and their esters, and ester gums.

Important cyclic and dicyclic unsaturated hydrocarbon monomer feeds containing about 5 to about 15 carbon atoms include cyclopentadiene and / or dicyclopentadiene and oligomers thereof. Although commercially available low-cost DCPD concentrates typically contain about 40 wt% to about 90 wt% DCPD, most preferred, however, very high purity DCPD in combination with olefinic modifier compounds may be used.

Olefin-based modifier compounds that can be used with cyclic and dicyclic unsaturated olefins include ethylene, propylene, butadiene, styrene, alpha-methyl styrene, vinyl toluene, indene, 1,3-pentadiene, isobutylene, isoprene, 1 Butenes, 1-hexene, 1-octene, limonene, alpha-pinene, beta-pinene, various acrylates and mixtures of these compounds. Olefinic modifier compound (s) are typically used in amounts ranging from about 0% to 35% by weight based on the total amount of cyclic and dicyclic unsaturated olefins and modifier compounds.

In addition to olefin modifiers, modified by rosin, distilled tall oil, fatty acids, dimer fatty acids, vegetable oils, phenolic compounds, maleic anhydride or fumaric acid, and combinations thereof are common. These may be added before, during or after the polymerization of the hydrocarbon based rosin. Furthermore, esterification of acid-modified rosin with polyols such as pentaerythritol and / or glycerin can be carried out to modify the rosin backbone based on hydrocarbons.

The above modified rosin, rosin derivatives and their esters or cyclic and dicyclic unsaturated olefin derived and / or modified / esterified resins can all be used as precursor resins for the process of the invention. Resins formed from one or more of these materials are well known in the art. Most preferred are high molecular weight / high solution viscosity resins having a solution viscosity in the range of about 10 to 75 bubble seconds at 38 ° C. These high molecular weight / high solution viscosity resins are typically branched, but are not inherently crosslinked. In the case of high molecular weight resins, the amount of crosslinking agent required to prepare the gelling resin by the process of the invention is typically minimized, although the chemical properties of the precursor resin affect the amount of crosslinking agent required.

An important feature in the process of the invention is the formation of covalent crosslinks in the ink resin in the absence of a metal-containing crosslinking agent. Thus, the precursor resin can be made to utilize inherent reactivity for self-crosslinking under the input of sufficient thermal energy for a sufficient time in the reaction chamber or to be able to use a nonmetal-containing crosslinking agent. Without the aid of a crosslinking agent, the time required to carry out the reaction is relatively long, and the final resin solution viscosity may be relatively insufficient compared to the same resin produced with the aid of a nonmetal containing crosslinking agent.

Suitable nonmetal-containing crosslinking agents include, but are not limited to, polycarboxylic acids such as fumaric acid, maleic anhydride, and dimer fatty acids, thermally reactive phenolic compounds, polyisocyanates, epoxy, silane coupling agents, and any of these Included are compounds selected from the group consisting of two or more mixtures. Of these, preferred crosslinking agents are thermally reactive phenolic compounds. These phenolic compounds are typically derived from phenols substituted with phenol or any of several alkyls or combinations of these phenols reacted with excess formaldehyde under base catalyzed conditions such that the final product is resinous and has residual methylol functionality. do. For example, phenol-formaldehyde resins used as base metal-containing crosslinkers can be prepared by reacting butyl-phenol and bisphenol-A with excess formaldehyde such that the resulting resin contains one or more reactive methylol groups.

The amount of crosslinking agent for forming the covalent crosslink is about 0.5 wt% to about 15 wt%, preferably about 1.0 wt% to about 5.0 wt%, more preferably about about the total amount of resin and crosslinking agent introduced into the reaction chamber. And may range from 1.25 wt% to about 3.0 wt%.

The crosslinking agent may be added to the resin to form a mixture and then supplied to a reaction vessel such as an extruder, or the crosslinking agent may be fed to the reaction vessel subsequent to the resin or simultaneously with the resin. Alternatively, the resin and the crosslinking agent may be bound under conditions that initiate but do not complete the crosslinking reaction, after which the partially crosslinked product in the reaction vessel is essentially sufficient time for the crosslinking reaction to complete to the desired degree. The partially crosslinked product can be further crosslinked by mixing while heating and heating to a temperature in the range of about 160 to about 300 ° C.

In a particularly preferred embodiment, the rosin or hydrocarbon based resin and from about 1.5 to about 3.0 wt% of crosslinking agent are deficient in an extruder having a plurality of zones arranged to produce subatmospheric pressure in at least one zone along the length of the extruder. Under the specified conditions. Multi-band twin screw extruders with counter-rotating or co-rotating engagement screws are particularly preferred devices for carrying out the method of the present invention. The term deficient will be understood to include the rate at which the resin is supplied to the reaction chamber in which all empty spaces in the reaction chamber are not filled with rosin. In at least one zone of the reaction chamber, preferably at a pressure lower than atmospheric pressure, the temperature of the resin supplied to the reaction chamber is preferably increased above 200 ° C. to about 275 ° C.

As an alternative to or in addition to operating a zone of the extruder under pressure below atmospheric pressure, one or more zones may provide a purge gas, preferably an inert gas, such as nitrogen, downstream of the purge gas zone. A vent may be provided for evacuating purge gas to one or more zones of and / or for applying a pressure below atmospheric pressure. In this way, water or byproduct gases can be removed from the extruder or discharged as the reaction proceeds.

As the precursor resin and the crosslinker pass through the extruder, they are mixed vigorously in one or more mixing zones, preferably at a temperature higher than the softening point of both the crosslinker and the precursor resin. It is important that the resin and crosslinker are thoroughly mixed while heating. During mixing and heating, a crosslinking reaction occurs in the resin to provide covalent crosslinking to the resulting product.

The at least partially gelled resin is preferably discharged from the outlet of the extruder at the temperature indicated by the pumping requirements of the extruder. Typically this means that the resin temperature is in the range of about 180 ° C to about 240 ° C. The resin may be divided into powder, chips, granules, flakes, etc. after exiting the exit end of the extruder, such as a highly viscous ribbon, sheet or rope, according to the die opening structure. Partially gelled resins have a Gardner bubble viscosity of generally greater than about 150 bubble seconds at 38 ° C. when discharged from the reaction chamber, which is considerably higher than conventional resins that can be used in ink vehicles. Those skilled in the art will readily recognize that resins having such a viscosity can be extremely difficult to produce with conventional stirred tank processing techniques.

In total, the crosslinking reaction does not need to be carried out under an inert gas atmosphere, but this inert gas atmosphere can be beneficial for some resins and can remove excessive coloring. Moreover, the reaction can be carried out under atmospheric pressure, under atmospheric pressure or under excessive pressure conditions. However, it is preferable to use one or more zones of the plurality of zone reaction chambers under pressure conditions lower than atmospheric pressure. The range of pressures is particularly preferably from about 250 mmHg to about 20 mmHg. Regardless of the pressure in the reaction chamber, it is important to keep the reactants mixed vigorously at a sufficiently high temperature for a time sufficient for the gelation level of the resin product to be achieved as expected.

A feature of the present invention is that high solution viscosity end products, which have not been achieved so far, are produced in a very short reaction time of about 0.5 minutes, typically from about 2 to about 5 minutes, with virtually uniform properties on a continuous basis. Can be.

The reacted and extruded product is typically from MAGIESOL 47/470 (Magies Brothers Chemicals, Fenjole, USA) in an amount ranging from about 10 wt% to about 50 wt%, based on the total amount of resin / solvent mixture. (Magie Brothers Chemical Company), a lithographic solvent such as linseed oil or soybean oil, wherein the gelling material is produced so that it can be added directly to the final ink composition with other ink components such as pigments, wax compounds and the like.

Although ink manufacturers may add crosslinking agents to the product at the time of vehicle compounding, this will generally not be required as the viscosity and properties of the product typically match or exceed the requirements that the ink manufacturer would achieve by adding a crosslinking agent. Thus, avoiding the time and cost associated with this additional step, the product obviates the need to add a crosslinking agent when preparing the final ink vehicle or ink composition. In addition, since the target viscosity is obtained based on the known properties of the ink resin itself, the need for gelation by the ink manufacturer is reduced, thus avoiding further modification in the ink resin properties.

The invention is described in detail with reference to the following non-limiting examples.

Examples 1-6

Various modified rosin ester precursor resins are available from the Schenectady Chemical Company of Schenectady, NY, SP-134, thermoreactive pure phenolic resins (phenol-formaldehyde containing reactive methylol groups). Resin) and in an extruder. Precursor rosin is specified in Table 1 below. The extruder was an 18 mm diameter co-rotating twin screw extruder available from Leistritz Corporation, Somerville, NJ, with one feed zone, one die zone and seven individual heating zones. . The temperature of the feed zone was kept at room temperature. The temperature of the first zone is 180 ° C .; The temperatures of the second, third and fourth zones are 250 ° C .; The fifth zone has a temperature of 250 ° C. and a nitrogen sparger; The sixth zone is at 250 ° C. and has a nitrogen vent; The temperature of the seventh zone is 225 ° C; The temperature of the die zone was 205 ° C. The resin and the phenolic crosslinking agent were dry blended as a powder and supplied to the extruder as it is. The screw speed was maintained at 150 RPM so that the residence time was about 5 minutes.

Table 1 shows the properties of the products with varying amounts of crosslinkers. Gelling resins commercially available with the properties of the resulting resins (Example 6, JONREZ RP-339 available from Westvaco Chemical Division of Westvaco Paper Company, Jacksonville, FL, USA) ) Compared to the characteristics of

The solution viscosity of the resin was measured in seconds by the Gardner bubble tube method, the softening point of the resin was measured according to ASTM Method E28-67, and the allowable amount of the resulting resin was 10 g of 33.3 wt% resin solution in linseed oil using MAGIESOL 47. It was determined by titration to the cloud point.

Example Number Resin Crosslinking agent (wt%) Final resin Final resin softening point (℃) Final resin solution viscosity ¹ (second) Final resin allowance ² (M47 mL) One One 2.00 19.1 200+ 322 12 2 2 1.00 15.9 200+ 620 17 3 3 2.00 19.2 200+ 500 6 4 4 1.00 15.6 200+ 489 60 5 5 11.75 14.3 200+ 180 13 Comparative Example 6 - - 18.6 168 128 7 ¹ 33.3 wt% resin solution in linseed oil. Viscosity recorded as Gardner bubble second at 38 ° C. ² Turbidity of 10 g of the solution titrated with MAGIESOL 47. Resin 1-Maleic acid modified rosin ester resin having a softening point of 153 ° C., an acid value of 18, a solution viscosity of 22 seconds and an allowable amount of 20 mL. Resin No. 2-a phenolic modified rosin ester resin having a softening point of 163 DEG C, an acid value of 20, a solution viscosity of 75 seconds, and an allowable amount of 25 mL. Resin 3-Phenol-based modified rosin ester resin having a softening point of 152 占 폚, an acid value of 20, a solution viscosity of 26 seconds, and an allowable amount of 10.5 mL. Resin No. 4-Phenol-based modified rosin ester resin having a softening point of 165 DEG C, an acid value of 20, a solution viscosity of 48 seconds, and an allowable amount of 200+ mL. Resin 5-Maleic acid modified rosin ester resin having a softening point of 136 DEG C, an acid value of 17.8, a solution viscosity of less than 5 seconds and an allowable amount of 125+ mL.

As shown in Table 1 above, resins prepared according to the process of the present invention have a much higher solution viscosity and generally larger final resin tolerance than JONREZ RP-339 resin (Example 6).

Example 7

Precursor-based resins derived from DCPD concentrate, rosin, distilled tall oil and maleic anhydride were crosslinked with an extruder. The starting resin had a solution viscosity of 12 seconds at 50 ° C. for 50 wt% MAGIESOL 47 solution and an allowable amount of MAGIESOL 47 was 6.5 mL. The extruder was an 18 mm diameter, nine-band interlocking co-rotating twinaxial machine available from Leaststreets, which was equipped with a ribbon die. 94 wt% hydrocarbon resin and 6 wt% dry powder blend of SP-134 were added at room temperature in an extruder with a feed zone. The reaction zone was set at 250 ° C. The nitrogen sparger was placed in the sixth zone of the extruder and the atmospheric vents were located in the seventh zone. The die zone temperature was maintained at 210 ° C. The final crosslinked resin had a softening point of 194.7 ° C., a solution viscosity of 50 wt% resin in MAGIESOL 47 at 38 ° C., 467 seconds, and an allowable amount of MAGIESOL 47 at 5 mL.

Examples 8 and 9

The crosslinked hydrocarbon based resin of Example 7 was used in a slab banash system to produce a high molecular weight commercial hydrocarbon resin (RESINALL 523 available from Resinall Corporation, Stamford, Conn.) Compared with. The varnish composition is shown in Table 2. The varnishes were evaluated in both ungelled or gelled states and the results are shown in Table 3 below.

ingredient Example 8 Resin of the Invention Example 9 Comparative Sample No. 1 RESINALL 523 Resin (wt%) 31.86 31.86 BECKACITE 4510 ³ (wt%) 16.99 16.99 S-84 # 3 alkyd ⁴ (wt%) 8.49 8.49 MAGIESOL 470 (wt%) 37.91 37.91 Tridecyl alcohol (wt%) 2.50 2.50 OAO ⁵ solution (wt%) 2.25 2.25 ³ BECKACITE 4510-A resin commercially available from Arizona Chemical Company, Panama City, FL, USA. ⁴ S-84 # 3-alkyd compound available from Bergvik Kemi AB, Sanderne, Sweden. ⁵ OAO-50 wt% oxyaluminum octoate in MAGIESOL 47.

characteristic Example 8 Resin of the Invention Example 9 Comparative Sample No. 1 (RESINALL 523) Before OAO crosslinker reaction After OAO crosslinker reaction Before OAO crosslinker reaction After OAO crosslinker reaction Viscosity 246.0 373.0 108.0 166.0 Yield value (dynes / cm ² ) 3016.0 11776.0 663.0 2165.0 Shortness Bee ⁶ 12.3 31.6 6.1 13.0 M47 allowance (mL) 5.0 13.5 10.5 14.0 ⁶ Shortness ratio = yield value / viscosity (measurement of gel structure)

As can be seen from Examples 8 and 9 above, the crosslinked hydrocarbon based resin of the present invention provides significantly higher viscosity and elasticity (yield) both before and after the gelling reaction as compared to Sample No. 1 of Example 9. It was. Likewise, the shortness ratios of varnishes made with the resins of the present invention were significantly higher than the corresponding shortness ratios of the varnishes of Example 9.

Examples 10, 11 and 12

To explain the latitude of the resin produced under various reaction conditions, maleic acid modified rosin esters were reacted with SP-134 under various reaction conditions. The precursor maleic acid modified rosin ester had an acid value of 18.7, a softening point of 154 ° C. and a solution viscosity of 18 seconds at 38 ° C. (33.3 wt% resin in linseed oil). The extruder was a co-rotating twin screw machine with a diameter of 40 mm available from Werner-Pfleiderer Corporation. The crosslinked resin containing the solid base metal was fed into the first zone at virtually room temperature. The molten precursor resin was fed into a second zone maintained at a temperature of 250 ° C. A series of eight zones, including the sixth and tenth zones with a pressure of about 100 mmHg below atmospheric pressure, were maintained at the reaction temperature of 275 ° C. and reactions were carried out using them. The last four zones were maintained at a temperature of 200 ° C. The resin exited the machine through the bottom discharge orifice. The results are shown in Table 4 below.

Example Number Precursor Supply Temperature (℃) Reaction temperature (℃) Screw RPM Processing Speed (kg / hr (lbs / hr)) Crosslinking agent content (wt%) Solution viscosity (33.3 wt%) 10 270 275 450 116.68 (257) 2.75 399 11 250 275 450 117.13 (258) 2.90 444 12 225 275 400 93.52 (206) 2.90 432

Examples 10-12 show that the resin can be added in a molten state to an extruder operated over a range of feed temperatures and processing speeds while still achieving the desired final resin viscosity. Comparing Examples 10 and 11, it can be seen that increasing the crosslinking agent from 2.75 wt% to 2.90 wt% can increase the viscosity by about 10%, even when the feed temperature drops from 270 ° C. to 250 ° C. The addition of molten resin can also result in faster processing speeds, as it eliminates the time spent melting the resin and raising the precursor resin / crosslinker mixture to the reaction temperature.

Examples 13-17

A series of pure phenolic resins were used to crosslink maleic acid modified rosin esters. The precursor resin was maleic acid modified rosin ester shown in Example 1 (Table 1). The extruder was a co-rotating twin screw extruder with a diameter of 18 mm and the operating conditions were similar to those used in Examples 1-5 (Table 1) except for the reaction time. The results are shown in Table 5 below.

Example Number Type of crosslinker (Shetectadi name) Crosslinking agent (wt%) Methylol content (wt% in crosslinking agent) Reaction temperature (℃) Final resin solution viscosity in seconds 13 HRJ-10518 5.0 7.5 250 195 14 SP-1045 3.0 9.3 275 183 15 SP-103 3.5 9.7 250 165 16 HRJ-1367 2.25 15.2 250 180 17 SP-134 2.25 14.9 235 344

As can be seen from Table 5 above, the phenolic resin-containing polyfunctional bisphenol-A (SP-134) gave the highest viscosity and lowest solubility due to its nonlinear structure. The reactivity of the crosslinker was shown to be a function of its methylol functional content. Thus, the crosslinker with more methylol content is converted to the less crosslinker needed to achieve the desired final resin solution viscosity.

Examples 18-20

Ink varnish formulations were prepared using high viscosity resins (Example 1 in Table 1), and conventional resins (comparative sample No. 2) and magnetic gelling resins (comparative sample No. 3) commercially available for comparison purposes. . The varnish formulations are shown in Table 6 below and the properties of the ink varnishes are shown in Table 7 below.

ingredient Example 18 Resin (wt%) of the Invention Example 19 Comparative Sample No. 2 (wt%) Example 20 Comparative Sample No. 3 (wt%) Resin (Example 1) 39.0 - - BECKACITE 6000 ⁷ - 38.7 - JONREZ RP-339 - - 39.0 S-84 # 3 alkyd 15.0 14.9 15.0 MAGIESOL 470 41.0 39.7 38.4 Tridecyl alcohol 5.0 4.8 7.6 OAO solution ⁸ - 2.0 - ⁷BECKACITE 6000 Resin commercially available from Arizona Chemical Company, Panama City, Florida, USA. ⁸ OAO solution-50 wt% oxyaluminum octoate in MAGIESOL 47.

characteristic Example 18 Resin of the Invention Example 19 Comparative Sample No. 2 Example 20 Comparative Sample No. 3 Laray viscosity 169 144 96 Yield value (dynes / cm ² ) 4996 3402 1810 Shortness ratio (yield value / viscosity) 29.6 23.6 18.9 MAGIESOL 47 Tall (TOL). 6.5 6.5 6.5

As indicated by the yield and shortness ratios, the resins of the present invention provide for the preparation of more structured ink varnishes (Example 18) than can be obtained using existing commercially available self-structuring resins (Example 20). Made it possible. In addition, in order to achieve the results provided by the resins of the present invention, addition of the crosslinking agent and subsequent gel reactions must be performed on the existing resins (Example 19).

Ink formulations were prepared using the ink varnish formulations of Examples 18, 19 and 20. The varnish formulations are shown in Table 8 below and the performance of the ink formulations in Table 9 below.

ingredient Example 18 Varnishes (g) of the Invention Example 19 Comparative Sample No. 2 (g) Example 20 Comparative Sample No. 3 (g) Varnish (prepared from the resin of Example 1) 12.75 - - BECKACITE 6000 ⁷ Varnishes - 12.75 - JONREZ RP-339 varnish - - 12.75 Blue Flush ⁹ 9.75 9.75 9.75 Wax Compound ¹⁰ 1.25 1.25 1.25 MAGIESOL 47 (adhesiveness adjustment) 0.75 0.50 0.40 ⁹ Blue Flush-Phthalocyanine GS Heat Fix Flush ¹⁰ Wax Compound-Heatset Wax Dispersion

characteristic Example 18 Varnishes of the Invention Example 19 Comparative Sample No. 2 Example 20 Comparative Sample No. 3 Average Glossiness ¹¹ (60 ° Angle) 46.40 46.0 46.4 Print density ¹² 2.34 2.36 2.38 Misting ¹³ 2 3 4 Adhesive ¹⁴ 12.0 12.0 12.0 ¹¹ Measured with Micro-tri-gloss Meter-BYK available from Gardener, Inc. of Silver Springs, Maryland, USA. ¹² Measured with COSAR SOS 40 densitometer available from Corsar Corporation, Dallas, Texas. ¹³ Incommeter determined at 1200 rpm and 32 ° C (0 = no misting, 10 = severe misting). ¹⁴ Measured with a Swing Albert electronic inometer at 1200 rpm and 32 ° C.

As shown in Table 9 above, the ink formulation containing the resin prepared according to the method of the present invention (Example 18) can be compared with ink formulations prepared with conventional resins and commercial self-gelling resins (Examples 19 and 20). Comparable varnish, print density and tack, but with lower misting properties. Thus, the ink resins made by the present invention may enable improved ink composition properties in terms of misting, which is believed to reflect the stronger gel structure of the resins associated with covalent crosslinking in the resins.

Example 21

Preparation of Reactive Rosin Base Resin

1000 g of tall oil resin was placed in a 3.785 liter (1 gallon) Parr autoclave reactor and heated to 160 ° C under nitrogen atmosphere to dissolve. Then, magnesium oxide (1.0 g) and bisphenol-A 76 g were added to the molten resin while stirring in a nitrogen atmosphere, and the temperature of the reactor was lowered to 120 ° C. After the contents of the reactor reached 120 ° C., 55 g of paraformaldehyde was mixed thereto. After sealing the reactor, the reaction was heated to 140 ° C. to maintain a pressure of about 393 kPa (57 psig) at this temperature for 3 hours.

The reaction was then placed in a three necked round bottom glass flask and heated to 190 ° C. to remelt. Then, maleic anhydride (30.0 g) was added thereto and the temperature of the reactor was maintained at 190 ° C. for 1 hour. After 1 hour, 120 g of glycerin was added to the reactor and the reactor temperature was raised to 260 ° C. and maintained at that temperature until the acid value of the reactants dropped to about 40 to 35 (ASTM D465-59). The reaction was then taken out and allowed to cool to room temperature. The cooled material was ground to a powder and observed to show that it had the following properties.

Acid Value: 34.1

Softening Point: 144.5 ℃

Gardner bubble viscosity at 38 ° C: 10 seconds

(33.3 wt% resin in linseed oil)

Magnetic crosslinking reaction

The resin prepared above was available from CW Brabender Instruments, Inc., a four-stage conical co-rotating twin screw extruder (CW Brabender Instruments, Inc. -30 series extruder), and the screw speed was 5 RPM. The first stage (feed) of the extruder was maintained at a temperature of about 140 ° C., the second stage was maintained at a temperature of about 275 ° C. and a pressure of about 100 mmHg, and the third stage was about 240 ° C., the fourth stage (die ) Was maintained at a temperature of about 140 ° C. The recovery of the product exiting the extruder was observed and the Gardner bubble viscosity for a 33.3 wt% solution in linseed oil was 100 bubble seconds.

Example 22

The phenolic modified rosin ester precursor resin, the resin of Example 2 (Table 1), was combined with 1.0 wt% maleic anhydride in an extruder. The extruder was an 18 mm diameter co-rotating twin-screw extruder available from Raystreets of Summerfill, NJ, with a feed zone, a die zone and seven separate heating zones. The temperature of the feed zone was kept at room temperature. The temperature of the first zone is 180 ° C; The second zone is 235 ° C; The third, fourth, fifth, and sixth zones were kept at 255 ° C., and the fifth zone had a nitrogen sparger; The sixth zone has a nitrogen vent; Seventh zone; The die zone was maintained at 225 ° C. The resin and the maleic anhydride crosslinking agent were dry blended as a powder and fed to the extruder as it is. The screw speed was maintained at 20 RPM and the residence time was about 15 minutes. The resulting resin had an acid value of 25.2, a softening point of 194.5 ° C., a solution viscosity of 120 seconds (33.3 wt% resin in flax oil), and an allowable amount of MAGIESOL 47 of 18 mL.

The foregoing description of specific embodiments of the invention has been described for illustrative purposes only, and it is understood that many modifications and variations can be made without departing from the spirit and scope of the invention as defined in the following claims. . While the embodiments described herein are the best mode known to the applicant in practicing the present invention, it will be understood that other methods of making high viscosity ink resins according to the claims are included in the present invention.

Claims (63)

A precursor resin selected from the group consisting of rosin and hydrocarbon based resins is introduced into the inlet of the extended reaction chamber, The precursor resin is run through the reaction chamber from its inlet end to the outlet, As the precursor resin proceeds through the reaction chamber, the precursor resin is continuously mixed while applying sufficient energy to the mixture with the nonmetal-containing crosslinking agent selected to induce the formation of covalent crosslinks in the resin, As the mixture proceeds while mixing through the reaction chamber, the mixture is heated at a specific temperature for a time sufficient to form covalent crosslinks in the mixture, to provide a stable high viscosity ink resin, A method of producing a high viscosity ink resin comprising discharging the ink resin from the outlet of the reaction chamber. The method of claim 1, wherein at least one portion of the reaction chamber is maintained at a pressure lower than atmospheric pressure. The method of claim 1, further comprising removing water from the reaction chamber when essentially water is formed. The method according to claim 1, wherein the precursor resin is a rosin-based resin consisting of an ester of modified rosin. The method of claim 1 wherein the precursor resin is a rosin-based resin consisting of a maleic acid modified rosin ester resin having a softening point of about 153 ° C., an acid value of about 18, a solution viscosity of about 22 seconds, and an allowable amount of 10 mL. The phenolic modified rosin according to claim 1, wherein the precursor resin has a softening point of about 150 to about 170 ° C., an acid value of about 20, a solution viscosity of about 20 to about 80 seconds, and an allowable amount of about 8 to about 200 mL. The method is a rosin-based resin consisting of an ester resin. The method of claim 1 wherein the precursor resin is a hydrocarbon based resin consisting of a functionalized cyclic or dicyclic unsaturated hydrocarbon resin derived from a hydrocarbon feed of about 5 to about 15 carbon atoms. The method of claim 1 wherein the crosslinker is a phenol-formaldehyde resin containing at least one reactive methylol group. The method of claim 1 wherein the crosslinker is derived from butyl phenol-bisphenol-A. The method of claim 1, wherein the temperature is in the range of about 150 to about 280 ° C. 3. The method of claim 1, wherein the precursor resin / crosslinker mixture occupies a volume less than the volume of the empty space of the reaction chamber. The method of claim 1 wherein the amount of crosslinking agent is in the range of about 0.5 to about 15 wt% based on the total amount of reactants. The method of claim 1 wherein the ink resin exiting the reaction chamber has a Gardner bubble viscosity at 38 ° C. of at least about 150 bubble seconds. A gelling resin produced by the method according to any one of claims 1 to 12. 15. An ink varnish based on claim 14, about 30 to about 60 wt%, phthalocyanine heatset flush about 20 to about 60 wt%, solvent about 1 to about 10 wt%, and wax dispersion about 1 to about Lithographic ink formulation comprising 10 wt%. Introducing a modified rosin based resin into the inlet of an extended reaction chamber having at least one mixing zone and at least one heating zone, The resin is run from its inlet end to the outlet through the mixing and heating zone of the reaction chamber, The resin is continuously mixed while applying a sufficient energy to the resin / crosslinker mixture as the mixture proceeds through the reaction chamber with the non-metal containing crosslinker selected to form covalent crosslinks in the resin in the mixing zone of the reaction chamber, As the mixture proceeds while mixing through the reaction chamber, the mixture forms covalent crosslinks in the mixture in the heating zone of the reaction chamber and gels at least partially in the reaction chamber of substantially increased viscosity for the resin initially introduced into the reaction chamber. Heated at a specific temperature for a time sufficient to provide a prepared ink resin, Draining the gelling resin from the outlet of the reaction chamber, The amount of crosslinking agent is from about 0.5 to about 15 wt%, based on the total amount of reactants, and the gardner bubble viscosity at about 38 ° C. of the resulting ink resin is about 180 to about 650 bubble seconds in a solution of about 33.3 wt% resin in linseed oil. Method of preparation. The method of claim 16, wherein the reaction chamber further has at least one water removal zone. 18. The method of claim 17, further comprising removing water from the reaction chamber in a water removal zone when essentially water is formed. 17. The process of claim 16 wherein the reaction chamber further comprises at least one sparging zone and at least one outlet zone for sparging an inert gas into the mixture as the mixture proceeds through the reaction chamber and withdrawing sparging gas from the reaction chamber. How to be. The method of claim 16, wherein at least one portion of the reaction chamber is maintained under pressure conditions below atmospheric pressure. The method of claim 16, wherein the modified rosin based resin comprises a partial ester of modified rosin. The resin of claim 16 wherein the resin of the modified rosin base comprises a maleic acid modified rosin ester resin having a softening point of about 153 ° C., an acid value of about 18, a solution viscosity of about 22 Gardner bubble seconds, and an allowable amount of 10 mL. Way. The resin of claim 16 wherein the resin of the modified rosin base has a softening point of about 150 to 170 ° C., an acid value of about 20, a solution viscosity of about 20 to about 80 Gardner bubble seconds, and an allowable amount in the range of about 8 to about 200 mL Phosphorus phenol-based modified rosin ester resin. The method of claim 16 wherein the crosslinker is a thermally reactive phenolic resin. The method of claim 16, wherein the crosslinker is a phenol-formaldehyde resin containing at least one reactive methylol group. The method of claim 16, wherein the temperature of the heating zone is in the range of about 150 to about 280 ° C. 18. The method of claim 16, wherein the resin / crosslinker mixture occupies a volume less than the volume of the empty space of the reaction chamber. An ink varnish composition comprising about 20 to about 60 wt% of a gelling resin according to any one of claims 16 to 27. The ink varnish of claim 28 comprising about 30 to about 50 wt%, phthalocyanine heat setting flush about 20 to about 60 wt%, solvent about 1 to about 10 wt%, and wax dispersion about 1 to about 10 wt% Slab Ink Formulations. Gelling ink varnish resin comprising reacting a precursor resin selected from the group consisting of rosin and hydrocarbon based resins with a non-metallic crosslinking agent to provide at least partially gelled resin having a Gardner bubble viscosity at about 38 ° C. of at least about 130 bubbles seconds Method of preparation. The method of claim 30 further comprising removing water from the reaction chamber during the polymerization reaction. 33. The method of claim 30, wherein at least one portion of the reaction chamber is maintained under pressure conditions below atmospheric pressure. The method of claim 30, wherein the precursor resin comprises an ester of modified rosin. The method of claim 30 wherein the precursor resin comprises a maleic acid modified rosin ester resin having a softening point of about 153 ° C., an acid value of about 18, a solution viscosity of about 22 seconds, and an allowable amount of 10 mL. The phenolic system of claim 30 wherein the precursor resin has a softening point of about 150 to about 170 ° C., an acid value of about 20, a solution viscosity of about 20 to about 80 seconds, and an allowable amount in the range of about 8 to about 200 mL. And a modified rosin ester resin. 31. The method of claim 30, wherein the crosslinker is a thermally reactive phenolic resin. 31. The method of claim 30, wherein the reaction is carried out at a temperature in the range of about 150 to about 280 ° C. 38. An ink varnish composition comprising about 20 to about 60 wt% of a gelling resin according to any one of claims 30 to 37. The ink varnish of claim 38 comprising about 30 to about 60 wt%, phthalocyanine heat setting flush about 20 to about 60 wt%, solvent about 1 to about 10 wt%, and wax dispersion about 1 to about 10 wt% Slab Ink Formulations. Introducing a hydrocarbon-based resin into the inlet of the extended reaction chamber, The resin proceeds through its reaction chamber from its inlet end towards the outlet, As the resin proceeds through the reaction chamber, the resin is continuously mixed while applying sufficient energy to the mixture with the nonmetal-containing crosslinking agent selected to induce the formation of covalent crosslinks in the resin, As the mixture proceeds while mixing through the reaction chamber, it forms covalent crosslinks in the mixture and heats the mixture at a certain temperature for a time sufficient to provide a substantially stable high viscosity ink resin, A method of producing a high viscosity ink resin comprising discharging the ink resin from the outlet of the reaction chamber. 41. The method of claim 40, wherein at least one portion of the reaction chamber is maintained under pressure conditions below atmospheric pressure. 41. The method of claim 40, further comprising removing water from the reaction chamber when essentially water is formed. 41. The method of claim 40, wherein the hydrocarbon based resin consists of a functionalized cyclic or dicyclic unsaturated hydrocarbon resin derived from a hydrocarbon feed of about 5 to about 15 carbon atoms. 41. The method of claim 40, wherein the crosslinker is a thermally reactive phenolic resin. 41. The method of claim 40, wherein the crosslinker is a phenol-formaldehyde resin containing at least one reactive methylol group. 41. The method of claim 40, wherein the temperature is in the range of about 150 to about 280 ° C. 41. The method of claim 40, wherein the resin / crosslinker mixture occupies a volume less than the volume of the empty space of the reaction chamber. The method of claim 40, wherein the amount of crosslinker is in the range of about 0.5 to about 15 wt% based on the total amount of reactants. The method of claim 40, wherein the ink resin exiting the reaction chamber has a Gardner bubble viscosity of at least about 150 bubbles seconds in a 50 wt% resin solution in MAGIESOL 47 at 38 ° C. 42. A gelling resin prepared by the method according to any one of claims 40 to 49. 41. An ink varnish based on the present invention comprising about 30 to about 60 wt%, phthalocyanine heat setting flush about 20 to about 60 wt%, solvent about 1 to about 10 wt%, and wax dispersion about 1 to about 10 wt% Slab Ink Formulations. Introducing a reactive precursor resin selected from the group consisting of a reactive rosin and a hydrocarbon based resin into the inlet of the extended reaction chamber, The reactive precursor resin is run through the reaction chamber from its inlet end toward the outlet, When the reactive precursor resin proceeds through the reaction chamber, the reactive precursor resin is heated at a certain temperature for a time sufficient to form covalent crosslinks in the resin and to provide a substantially stable high viscosity ink resin, A method of producing a high viscosity ink resin comprising discharging the ink resin from the outlet of the reaction chamber. 53. The method of claim 52, wherein the material selected from the group consisting of rosin, rosin ester, cyclopentadiene, dicyclopentadiene, and the like, is functionalized with sufficient thermal energy for a sufficient time so that the intrinsic reactivity in the precursor resin to crosslinking is available. To produce a reactive precursor resin. 53. The reactive precursor of claim 52, wherein a material selected from the group consisting of rosin, rosin ester, cyclopentadiene, dicyclopentadiene, and the like, is combined with a nonmetallic crosslinking agent prior to introducing the reactive precursor material into the inlet of the extended reaction chamber. Further comprising preparing a resin. The method of claim 54, wherein the crosslinking agent is combined with the precursor resin in an amount in the range of from about 0.5 to about 15 wt% based on the total amount of reactants. 55. The method of claim 54, wherein the nonmetallic crosslinking agent is a thermally reactive phenolic resin. The method of claim 56 wherein the crosslinker is a phenol-formaldehyde resin containing at least one reactive methylol group. 53. The method of claim 52, wherein at least one portion of the reaction chamber is maintained under pressure conditions below atmospheric pressure. 53. The method of claim 52, wherein the temperature is in a range from about 150 to about 280 ° C. The method of claim 52, wherein the reactive precursor resin occupies a smaller volume than the volume of the void space of the reaction chamber. 53. The method of claim 52, wherein the ink resin exiting the reaction chamber has a Gardner bubble viscosity of at least about 150 bubble seconds at 38 ° C. A gelling resin prepared by the method according to any one of claims 52 to 61. The ink varnish of claim 62 comprising about 30 to about 60 wt%, phthalocyanine heat setting flush about 20 to about 60 wt%, solvent about 1 to about 10 wt%, and wax dispersion about 1 to about 10 wt% Slab Ink Formulations.